CN109550405A - A kind of ion selectivity polymer includes the preparation method and applications of film - Google Patents
A kind of ion selectivity polymer includes the preparation method and applications of film Download PDFInfo
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- CN109550405A CN109550405A CN201811416700.3A CN201811416700A CN109550405A CN 109550405 A CN109550405 A CN 109550405A CN 201811416700 A CN201811416700 A CN 201811416700A CN 109550405 A CN109550405 A CN 109550405A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28038—Membranes or mats made from fibers or filaments
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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Abstract
The invention discloses the preparation method and applications that a kind of ion selectivity polymer includes film, belong to light-duty chemical field.The present invention is using Triafol T as polymer substrate, and Surfactin is ionophore, and it includes film that 2- nitrobenzophenone n-octyl ether and trioctyl phosphate etc., which prepare polymer for plasticizer,.Polymer obtained includes that film character is stable, ion selectivity is preferable, useful life longevity is preferable and is easily recycled, and has great energy-saving and emission-reduction and environmental-friendly advantage.
Description
Technical field
The present invention relates to the preparation method and applications that a kind of ion selectivity polymer includes film, belong to light-duty chemical industry neck
Domain.
Background technique
In recent years, it is discharged into sewage largely containing heavy metal in natural water, leads to the water environment of river, lake, ocean
Deteriorate.Heavy metal is difficult to degrade and toxic, can jeopardize the life of the mankind.Heavy metal pollution in water world wide be one compared with
For universal safety problem, the often more difficult removal of these metal ions, traditional side using solution extraction and separation metal ion
Method can consume the resources such as a large amount of reagents, and cost performance is not high.In order to improve the efficiency for being separated from the water metal ion, and reduces and divide
From resource consumption in the process, people have attempted many membrane separation techniques in the past few decades, these membrane separation techniques have
High transmitting flux and good selectivity, can efficiently separate the metal ion in water.
But in these membrane separation techniques, currently used is supported liquid membrane (SLM) and bulk liquids film (BLM),
In, SLM haves the shortcomings that stability is poor and the service life is insufficient, and the solvent on film can gradually lose and be dissolved in water in use
Xiang Zhong causes secondary pollution, is unfavorable for its popularization and application in the industry；BLM higher operating costs, in terms of economic cost not
It is able to satisfy the demand of commercial production level.
Polymer includes that film (PIM) is a kind of emerging film base isolation technics, and PIM has higher selectivity to metal ion
And wider application range, and its with good stability and useful life longevity, thus in point of commercial metal waste water
From there is good development potentiality in processing.
Polymer in the preparation process of film (PIM) comprising often selecting macrocyclic compound as ionophore, macrocyclic compound
Inner cavity aperture with specific dimensions, is capable of combination of the realization of selectivity to object, and the property of can choose identifies metal ion.?
In research process before, inventors have found that many big ring carriers are poor to the selectivity of metal ion, and there are difficult to degrade and
The various problems such as toxicity.
Summary of the invention
To solve the above-mentioned problems, the present invention provides the polymer that a kind of pair of metal ion has selective removal performance
Preparation method and application comprising film.The present invention utilizes the cavity structure energy of Surfactin (sodium bacillus subtilis lipopeptide) particular size
The characteristics of enough selective binding metal ions, selection Surfactin are ionophore, and Triafol T is polymer substrate,
Plasticizer is added to prepare polymer comprising film, the polymer prepared includes that film has good ion selectivity, especially right
Pb2+With very strong selectivity.The ionophore that the present invention selects has the characteristics that biodegradable and toxicity is low, can reach ring
The purpose of border close friend, and film is not in use loss substantially, can be used repeatedly, save cost.
The first purpose of the invention is to provide the preparation method that a kind of ion selectivity polymer includes film, the methods
It is that polymer substrate, Surfactin, plasticizer are uniformly mixed to obtained casting solution, the solvent of the casting solution is methylene chloride
Or chloroform, casting solution is poured into reactor and is horizontally arranged, to include film after solvent volatilization up to polymer,
In, the Surfactin is sodium bacillus subtilis lipopeptide, and molecular formula is as shown in formula I:
Wherein, n=2,3 or 4.
In one embodiment of the invention, the polymer substrate is for solvent, concentration 4-20g/
L。
In one embodiment of the invention, the mass ratio of the Surfactin and polymer substrate is 2:(0.5-
20)。
In one embodiment of the invention, quality (mg) volume (μ L) ratio of the polymer substrate and plasticizer is
2:(1-15).
In one embodiment of the invention, the polymer substrate is Triafol T (CTA) or acetate fiber
Plain (CA).
In one embodiment of the invention, the plasticizer is 2- nitrobenzophenone n-octyl ether (NPOE), decanedioic acid
Any one of dibutyl ester, dioctyl phthalate or trioctyl phosphate.
In one embodiment of the invention, the plasticizer is preferably 2- nitrobenzophenone n-octyl ether (NPOE).
In one embodiment of the invention, the method is that polymer substrate is configured to concentration for 4-20g/L
Surfactin and plasticizer is added in polymer substrate mother liquor in mother liquor, is stirred at room temperature uniformly, later falls mixture
Enter in reactor, be horizontally arranged, taken off after naturally dry or drying, be can be obtained poly- with a thickness of 2-30 μm of ion selectivity
Closing object includes film；Wherein, the mass ratio of the Surfactin and polymer substrate is 2:(0.5-20)；The polymer substrate
Quality mg volume μ L ratio with plasticizer is 2:(1-15).
In one embodiment of the invention, the solvent of the polymer substrate mother liquor is methylene chloride or three chloromethanes
Alkane.
A second object of the present invention is to provide the applications that the polymer includes film.
In one embodiment of the invention, the application is the application in field of waste water treatment, is especially being polluted
The application of the removal of heavy metal in waste liquid ion and recycling aspect.
In one embodiment of the invention, the heavy metal ion is Cu2+、Pb2+、Co2+、Fe3+、Ni2+、Cr3+Deng
One or more of heavy metal ion.
Beneficial effects of the present invention:
(1) present invention use Triafol T or cellulose acetate for polymer substrate, NPOE be plasticizer, surface work
Property element be ionophore prepare polymer include film, Triafol T or cellulose acetate biological degradability are excellent, thermostabilization
Property is good；NPOE plasticization effect is good, and is in use substantially not in leakage；Surfactin biological degradability
Excellent and toxicity is low.The polymer prepared includes that film is easy to degrade, and has the advantages that good regenerability and environmental-friendly,
The stability and good mechanical performance of film simultaneously.
(2) the method for the present invention is simple, easy to operate, by the method for the present invention obtain polymer include film to metal ion have compared with
Good ion selectivity, and there is selectivity to most metal ions.Wherein Pb2+、Ni2+、Ca2+、Cu2+、Co2+、Mg2+In film
On membrane flux be respectively 0.325 μm of ol/ (m2·s)、0.498μmol/(m2·s)、0.486μmol/(m2·s)、0.222μ
mol/(m2·s)、0.414μmol/(m2·s)、0.148μmol/(m2·s)。
(3) polymer of the invention includes that film is applied widely, in temperature range room temperature~50 DEG C, pH range 3~7
It can use, and there is selectivity to most metal ions.
(4) polymer of the invention includes film during the entire process of metal ion transmits, and the structure of metal ion does not have
It is destroyed, and the structure of film does not also change, can repeatedly use, useful life longevity is excellent.
Detailed description of the invention
Fig. 1: polymer includes film thermogravimetric analysis figure；
Fig. 2: (wherein CTA is Triafol T to infared spectrum of the different component polymer comprising film, NPOE is 2- nitro
Phenyl n-octyl ether, SF are Surfactin)；
Fig. 3: H-type ion exchange pond；
Fig. 4: different metal ions is in the membrane flux that the polymer that embodiment 1 is prepared includes on film；
Fig. 5: the polymer that embodiment 1 is prepared includes adsorption capacity of the film to different metal ions；
Fig. 6: the polymer that embodiment 1 is prepared includes adsorption capacity of the film to mixed metal ion.
Specific embodiment
Embodiment 1: polymer includes the preparation of film
It includes film that polymer, which is prepared as follows:
(1) preparation of Triafol T mother liquor: taking 5g Triafol T (White crystalline solid), and three chloromethanes are added
Alkane solvents are settled to 500mL, are stirred at room temperature half an hour and dissolve it sufficiently, and 10g/L Triafol T mother liquor is made.
(2) polymer includes the preparation of film: 30mg Surfactin is added to 75 μ L 2- nitrobenzophenone n-octyl ethers
In 5mL Triafol T mother liquor, being stirred at room temperature half an hour is made it dissolve.Obtained casting solution is poured into reactor,
Reactor water placing flat, include film after it volatilizees naturally up to polymer.
Fig. 1 is the thermogravimetric analysis figure that the polymer that embodiment 1 is prepared includes film, and polymer includes film to 200 DEG C
It is above just to start decomposing phenomenon occur, illustrate that thermostabilization of the polymer comprising film is preferable, using basic under normal temperature range
It is not in problem.
Fig. 2 is the infrared spectrogram that the polymer that different component is prepared includes film, and wherein embodiment 1 is prepared
Absorption peak all in existing CTA film infrared spectrogram in the infrared spectroscopy of CTA-NPOE-SF film, and have CTA-NPOE film infrared
All absorption peaks in spectrogram.Illustrate to truly have ingredient CTA and NPOE in CTA-NPOE-SF film.In addition to this, CTA-NPOE-
The infrared spectroscopy of SF film characteristic peak of an amide more than CTA-NPOE film infrared spectrogram at the 1653cm-1, illustrates surface
Active extract (SF) has been added in the structure of film, and there is no any chemical reactions on film.
Embodiment 2: polymer includes the preparation of film
It includes film that polymer, which is prepared as follows:
(1) preparation of Triafol T mother liquor: taking 5g Triafol T (White crystalline solid), and three chloromethanes are added
Alkane solvents are settled to 500mL, are stirred at room temperature half an hour and dissolve it sufficiently, and 10g/L Triafol T mother liquor is made.
(2) polymer includes the preparation of film: 40mg Surfactin is added to 75 μ L 2- nitrobenzophenone n-octyl ethers
In 5mL Triafol T mother liquor, being stirred at room temperature half an hour is made it dissolve.Obtained casting solution is poured into reactor,
Reactor water placing flat, include film after it volatilizees naturally up to polymer.
Embodiment 3: polymer includes the preparation of film
It includes film that polymer, which is prepared as follows:
(1) preparation of Triafol T mother liquor: taking 5g Triafol T (White crystalline solid), and three chloromethanes are added
Alkane solvents are settled to 500mL, are stirred at room temperature half an hour and dissolve it sufficiently, and 10g/L Triafol T mother liquor is made.
(2) polymer includes the preparation of film: 20mg Surfactin and 75 μ L trioctyl phosphates are added to 5mL tri- acetic acid fibre
It ties up in plain mother liquor, being stirred at room temperature half an hour makes it dissolve.Obtained casting solution is poured into reactor, reactor level
It places, includes film after it volatilizees naturally up to polymer.
Embodiment 4: polymer includes the preparation of film (CTA mother liquid concentration is different)
(1) preparation of Triafol T mother liquor: taking 1g Triafol T (White crystalline solid), and three chloromethanes are added
Alkane solvents are settled to 500mL, are stirred at room temperature half an hour and dissolve it sufficiently, and 2g/L Triafol T mother liquor is made.
(2) polymer includes the preparation of film: 30mg Surfactin is added to 75 μ L 2- nitrobenzophenone n-octyl ethers
In 5mL Triafol T mother liquor, being stirred at room temperature half an hour is made it dissolve.Obtained casting solution is poured into reactor,
Reactor water placing flat, include film after it volatilizees naturally up to polymer.
Embodiment 5: polymer includes the preparation (substituting CTA using CA) of film
(1) preparation of cellulose acetate mother liquor: taking 5g cellulose acetate, and dichloromethane solvent is added and is settled to 500mL,
Stirring half an hour dissolves it sufficiently at room temperature, and 10g/L cellulose acetate mother liquor is made.
(2) polymer includes the preparation of film: 30mg Surfactin is added to 75 μ L 2- nitrobenzophenone n-octyl ethers
In 5mL cellulose acetate mother liquor, being stirred at room temperature half an hour is made it dissolve.Obtained casting solution is poured into reactor,
Reactor water placing flat includes film after it volatilizees naturally up to polymer.
Embodiment 6: polymer includes application of the film in separation underwater gold category ions
Include that be placed in H-type electrolytic cell (Fig. 3) intermediate and with clamp for film by polymer that embodiment 1 is prepared, is electrolysed
It is the different types of metal-nitrate solutions of 20mg/L that 50mL concentration is separately added on the left of pond, and right side is added 50mL concentration and is
The dilute nitric acid solution of 0.1mol/L, is stirred at room temperature, and measures after 24 hours and calculates membrane flux of the metal ion on film.Such as
Shown in Fig. 4, Pb2+、Ni2+、Ca2+、Cu2+、Co2+、Mg2+Membrane flux on film is respectively 0.325 μm of ol/ (m2·s)、0.498μ
mol/(m2·s)、0.486μmol/(m2·s)、0.222μmol/(m2·s)、0.414μmol/(m2·s)、0.148μmol/
(m2S), it is seen then that the polymer that embodiment 1 is prepared includes the adsorbing metal ions that film is capable of selectivity.
Embodiment 7: polymer includes the application of film absorption underwater gold category ions
The polymer for taking 10mg embodiment 1 to be prepared includes that film is respectively placed in the different types of gold of 50mL 20mmol/L
In genus nitrobacter solution.It is stirred at room temperature, is measured after 24 hours and calculates adsorption capacity of the metal ion on film, such as Fig. 5
Shown, polymer includes film to Pb2+Adsorption capacity up to 40mg/g or more, and to Fe3+、Cu2+、Co2+Also there is higher absorption
Content, it is seen that the polymer that the present invention is prepared include film can selective absorption metal ion, and its suction to lead ion
Attached ability is stronger.
Embodiment 8: polymer includes the application of film absorption underwater gold category ions
It is 20mmol/L Pb that the polymer for taking 10mg embodiment 1 to be prepared, which is placed in 50mL concentration comprising film,2+、Fe3+、
Ni2+、Ca2+、Cu2+、Co2+、Mg2+In different types of metal mixed nitrate solution.It is stirred at room temperature, is measured after 24 hours
And adsorption capacity of the metal ion on film is calculated, as shown in Figure 6, it is seen then that polymer includes film to Pb2+Adsorption capacity it is reachable
25mg/g or more, and to Fe3+、Ni2+、Cu2+、Co2+Deng also there is absorption, it is seen that the polymer that the present invention is prepared includes film energy
Enough selective absorption metal ions, and it is stronger to the adsorption capacity of lead ion.
Embodiment 9: polymer is tested comprising film useful life longevity
Having studied polymer includes influence of the film reuse to its film properties, lead ion membrane flux table on film properties film
Show, after reusing 5 times, polymer includes seldom (less than 5%) of film properties decline, and result of study illustrates that polymer includes
The access times of film influence very little to its ion selectivity, and film has preferable useful life longevity.
Embodiment 10: polymer includes application of the film in separation underwater gold category ions under high-temperature condition
Include that be placed in H-type electrolytic cell (Fig. 3) intermediate and with clamp for film by polymer that embodiment 1 is prepared, is electrolysed
It is the different types of metal-nitrate solutions of 20mg/L that 50mL concentration is separately added on the left of pond, and right side is added 50mL concentration and is
The dilute nitric acid solution of 0.1mol/L.It is stirred at 45 DEG C, measured after 24 hours and calculates membrane flux of the metal ion on film.Knot
Fruit is as shown in table 1, and under high temperature, the ion selectivity of film, there is no significant change, shows this with ion selectivity at room temperature
The polymer of invention preparation includes that film can be used normally at room temperature~50 DEG C.
1 polymer of table includes the membrane flux of different metal ions of the film at 45 DEG C
| Metal ion | Pb(II) | Co(II) | Cu(II) | Ni(II) | Ca(II) | Mg(II) |
| Membrane flux (μm ol/ (m2s)) | 0.328 | 0.420 | 0.220 | 0.492 | 0.482 | 0.156 |
Comparative example 1: polymer includes the preparation (using polyvinyl chloride) of film
(1) preparation of polychloroethylene mother liquor: taking 5g polyvinyl chloride, and chloroform solvent is added and is settled to 500mL, in room temperature
Lower stirring half an hour dissolves it sufficiently, and 10g/L polychloroethylene mother liquor is made.
(2) polymer includes the preparation of film: 30mg Surfactin is added to 75 μ L 2- nitrobenzophenone n-octyl ethers
In 5mL polychloroethylene mother liquor, being stirred at room temperature half an hour is made it dissolve.Obtained casting solution is poured into reactor, anti-
It answers device horizontal positioned, includes film after it volatilizees naturally up to polymer.
Comparative example 2
(1) preparation of Triafol T mother liquor: taking 5g Triafol T, and chloroform solvent is added and is settled to
500mL, being stirred at room temperature half an hour dissolves it sufficiently, and 10g/L Triafol T mother liquor is made.
(2) polymer includes the preparation of film: 5mg Surfactin and 75 μ L 2- nitrobenzophenone n-octyl ethers are added to 5mL
In Triafol T mother liquor, being stirred at room temperature half an hour is made it dissolve.Obtained casting solution is poured into reactor, anti-
It answers device horizontal positioned, includes film after it volatilizees naturally up to polymer.
Comparative example 3: polymer includes the preparation of film
(1) preparation of Triafol T mother liquor: taking 12g Triafol T, and chloroform solvent is added and is settled to
500mL, being stirred at room temperature half an hour dissolves it sufficiently, and 24g/L Triafol T mother liquor is made.
(2) polymer includes the preparation of film: 30mg Surfactin is added to 75 μ L 2- nitrobenzophenone n-octyl ethers
In 5mL Triafol T mother liquor, being stirred at room temperature half an hour is made it dissolve.Obtained casting solution is poured into reactor,
Reactor water placing flat, include film after it volatilizees naturally up to polymer.
The film that comparative example 1,2,3 is prepared in the way of embodiment 6 is tested for the property, lead on film properties film
Ion membrane flux indicates, test result is as follows table 2, as seen from the above table, only using acetate fiber and triacetate fiber as gathering
The polymer that polymer matrix is prepared includes that the membrane flux of film is bigger, has stronger ion selectivity.
2 comparative example 1-3 polymer of table includes the membrane flux of lead ion on film
| Sample | Embodiment 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Lead ion membrane flux (μm ol/ (m2s)) | 0.325 | 0.075 | 0.278 | 0.254 |
Although the present invention has been described by way of example and in terms of the preferred embodiments, it is not intended to limit the invention, any to be familiar with this skill
The people of art can do various change and modification, therefore protection model of the invention without departing from the spirit and scope of the present invention
Enclosing subject to the definition of the claims.
Claims (10)
1. a kind of ion selectivity polymer include film preparation method, which is characterized in that the method be by polymer substrate,
Surfactin, plasticizer are uniformly mixed obtained casting solution, and the solvent of the casting solution is dichloromethane or chloroform, casting
Film liquid is poured into reactor and is horizontally arranged, to include film after solvent volatilization up to polymer；Wherein, the Surfactin
As sodium bacillus subtilis lipopeptide, molecular formula is as shown in following formula I:
Wherein, n=2,3 or 4.
2. the preparation method that a kind of ion selectivity polymer according to claim 1 includes film, which is characterized in that described
Polymer substrate is Triafol T or cellulose acetate, and the concentration relative to solvent is 4-20g/L.
3. the preparation method that a kind of ion selectivity polymer according to claim 1 or 2 includes film, which is characterized in that
The mass ratio of the Surfactin and polymer substrate is 2:(0.5-20).
4. a kind of ion selectivity polymer according to claim 1 to 3 includes the preparation method of film, feature exists
In the ratio of the polymer substrate and plasticizer is 2mg:(1-15) μ L.
5. a kind of ion selectivity polymer according to claim 1 to 4 includes the preparation method of film, feature exists
In the plasticizer is 2- nitrobenzophenone n-octyl ether (NPOE), dibutyl sebacate, dioctyl phthalate or tricresyl phosphate
Any one of monooctyl ester.
6. a kind of -5 any ion selectivity polymer include the preparation method of film according to claim 1, feature exists
In the method is: polymer substrate being configured to the polymer substrate mother liquor that concentration is 4-20g/L, table is added in mother liquor
Face active extract and plasticizer are stirred at room temperature uniformly, pour the mixture into reactor later, are horizontally arranged, naturally dry
Or taken off after drying, can be obtained with a thickness of 2-30 μm of ion selectivity polymer includes film；Wherein, the surface-active
The mass ratio of element and polymer substrate is 2:(0.5-20)；The ratio of the polymer substrate and plasticizer is 2mg:(1-15) μ
L。
7. the preparation method that a kind of ion selectivity polymer according to claim 6 includes film, which is characterized in that described
The solvent of polymer substrate mother liquor is dichloromethane or chloroform.
8. a kind of ion selectivity polymer as claimed in claim 1 to 7 includes the ion that the preparation method of film is prepared
Selective polymerisation object includes film.
9. ion selectivity polymer according to any one of claims 8 includes application of the film in field of waste water treatment.
10. application according to claim 9, which is characterized in that the application is that ion selectivity polymer includes that film exists
The removal and the application of recycling aspect of heavy metal in waste liquid ion are polluted, wherein heavy metal ion is Cu2+、Pb2+、Co2+、Fe3+、
Ni2+Or Cr3+One or more of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811416700.3A CN109550405B (en) | 2018-11-26 | 2018-11-26 | Preparation method and application of ion selective polymer containing membrane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811416700.3A CN109550405B (en) | 2018-11-26 | 2018-11-26 | Preparation method and application of ion selective polymer containing membrane |
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| Publication Number | Publication Date |
|---|---|
| CN109550405A true CN109550405A (en) | 2019-04-02 |
| CN109550405B CN109550405B (en) | 2020-08-04 |
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| CN112480448A (en) * | 2020-12-10 | 2021-03-12 | 江南大学 | Preparation method and application of metal ion transmission polymer containing membrane |
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| CN112480448B (en) * | 2020-12-10 | 2021-10-22 | 江南大学 | Preparation method and application of metal ion transmission polymer containing membrane |
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